(Perfluoro)alkylsilyl-Substituted 2-[Bis(4-aryl)phosphino]pyridines: Synthesis and Comparison of Their Palladium Complexes in Methoxycarbonylation of Phenylacetylene in Regular Solvents and Supercritical CO<sub>2</sub>
作者:Jeroen. J. M. de Pater、C. Elizabeth P. Maljaars、Elwin de Wolf、Martin Lutz、Anthony L. Spek、Berth-Jan Deelman、Cornelis J. Elsevier、Gerard van Koten
DOI:10.1021/om050479+
日期:2005.10.1
derived from [Pd(OAc)2] as the palladium source with either 9 or 10 as ligand showed the same activity (TON = 4000, 50 min reaction time) and selectivity (about 98% for the branched product) as the catalyst obtained from [Pd(OAc)2] and 2-[diphenylphosphino]pyridine (2). Both 2 and 10 were also tested in this reaction using a 1:1 mixture of methanol and α,α‘,α‘ ‘-trifluorotoluene as solvent system: fluorous
三种新的2- [双4-(溴)苯基}膦基]吡啶(8),2- [双4-(三甲基甲硅烷基)苯基}膦基]吡啶(9)和2- [双报道了4-((2-(全氟己基乙基)乙基)二甲基甲硅烷基)苯基}膦基]吡啶(10)配体(L)。相应的化合物的反式- /顺- [的PdCl 2(L)2 ] 11 - 13,反式- [的PdCl(ME)(L)2 ] 14 - 16,和马来酸酐配合物[加入Pd(L)2(环- ( -CH CHC(O)OC(O)-)] 17和合成并表征了18种。在甲醇中苯乙炔的甲氧基羰基化反应中,衍生自[Pd(OAc)2 ]作为钯源的钯或9或10配体表现出相同的活性(TON = 4000,反应时间为50分钟)和选择性(对于Pd(OAc)2为50%,选择性约为98%)。由[Pd(OAc)2 ]和2- [二苯基膦基]吡啶(2)获得的作为催化剂的支链产物)。既2和10也被在此反应中,使用1测试:甲醇和